Mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives

ABSTRACT

Described are mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives having the generic structure: ##STR1## wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond; wherein R 1 , R 1  &#39;, R 1  &#34;, R 1  &#39;&#34;, R 1  &#34;&#34;, R 3 , R 5 , R 5  &#39;, R 5  &#34;, R 5  &#39;&#34;, R 5  &#34;&#34; and R 6  represent hydrogen or methyl with the provisos: 
     (i) at least four of R 1 , R 1  &#39;, R 1  &#34;, R 1  &#39;&#34; and R 1  &#34;&#34; are hydrogen; and (ii) at least four of R 5 , R 5  &#39;, R 5  &#34;, R 5  &#39;&#34; and R 5  &#34;&#34; represent hydrogen; 
     and wherein Z represents one of the moieties: 
     (i) carboxaldehyde having the structure: ##STR2## (ii) alkylene dioxy or dialkoxy methyl having the structure: ##STR3## (iii) hydroxy methyl having the structure: ##STR4## (iv) acetoxymethyl having the structure: ##STR5##  and wherein R 7  and R 8  taken separately represent C 1  -C 4  lower alkyl or R 7  and R 8  taken together represent C 2  -C 4  alkylene; wherein the line represented by: 
     
         [++++] 
    
      is either (i) a carbon-carbon single bond when R 7  and R 8  taken together are C 2  -C 4  alkylene or (ii) no bond at all when R 7  and R 8  taken separately represent C 1  -C 4  lower alkyl. Also described are processes for preparing such mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives, and processes for using the above defined mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives for their organoleptic properties and compositions containing said mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives including perfumes, perfumed articles (such as solid or liquid anionic, cationic, nonionic or zwitterionic detergents, perfumed polymers, fabric softeners and cosmetic powders), foodstuffs, chewing gums, toothpastes, medicinal products, chewing tobaccos, smoking tobaccos and smoking tobacco articles.

This is a divisional of application Ser. No. 354,387, filed Mar. 2, 1982.

BACKGROUND OF THE INVENTION

Materials including mixtures of natural products which can provide, augment or enhance melony, cucumber, violet-like, green, leafy green, herbaceous, wormwood-like, floral, cinnamic, sandalwood-like, patchouli-like, vetiver-like, sweaty, animalic and spicy fragrance notes are known in the art of perfumery. Many of the natural materials which provide such fragrances and contribute desired nuances to perfumery compositions are high in cost, vary in quality from one batch to another and/or are generally subject to the usual vibrations in the natural products.

There is, accordingly, a continuing effort to find synthetic materials which will replace the essential fragrance notes provided by such natural essential oils or compositions thereof. Unfortunately, many of these synthetic materials either have the desired nuances only to a relatively small degree or else contribute undesirable or unwanted odor to the perfume compositions, perfumed articles or colognes using the same. The search for materials which can provide a more refined patchouli-like fragrance, for example, or a more refined floral fragrance, for example, or combination thereof ("floral/patchouli") has been difficult and relatively costly in the areas of both natural products and synthetic products.

In addition, artificial flavoring agents for foodstuffs have received increasing attention in recent years. For many years, such food flavoring agents have been preferred over natural flavoring agents at least in part due to their diminished costs and their reproducible flavor qualities. For example, natural food flavoring agents such as extracts, concentrates and the like are often subject to wide variations due to changes in quality, and type and treatment of the raw materials. Such variations can be reflected in the end product and result in unfavorable flavor characteristics in said end product. Additionally, the presence of the natural product in the ultimate food may be undesirable because of increased tendency to spoil. This is particularly troublesome in food and food uses where such products as dips, soups, chips, saugages, gravies and the like are apt to be stored prior to use.

The fundamental problem in creating artificial flavor agents is that the artificial flavor to be achieved be as natural as possible. This generally proves to be a difficult task since the mechanism for flavor development in many foods is not completely known. This is noticeable in products which have orange flavors, mint flavors, peppermint flavors, and even artichoke-like flavors and corresponding aroma characteristics.

Thus, reproduction of sweet, aldehydic, floral, melony, herbaceous, green, and artichoke-like aroma and taste characteristics has been the subject of long and continuing searches by those engaged in the production of foodstuffs and beverages. The severe shortage of food in many parts of the world has given rise to the development of previously unused sources of protein which have heretofore been unpalatable. Accordingly, the need has arisen for the use of flavoring materials which will make such sources of protein palatable to human sensory organs.

The use of tricyclohydrocarbyl oxomethyl derivatives is known in the art of perfumery. Thus, U.S. Pat. No. 4,123,394 issued on Oct. 31, 1978 discloses specifically the compound having the structure: ##STR6## and generically the compound having the structure: ##STR7## wherein R₈ ' is hydrogen, acyl, alkyl or alkenyl.

French Pat. No. 2,424,244 (corresponding to British Patent Application No. 2,019,841) discloses 8-exo-hydroxymethyl-endo-tricyclodecanes useful as perfumery agents in soaps, shampoos, cosmetics and waxes wherein the fragrances range from green, green grass-like, fruit-like to wood-like. The generic structure of the compounds disclosed in French Pat. No. 2,424,244 (assigned to the Kao Soap Company of Japan) is: ##STR8## wherein R is unsaturated C₁ -C₅ alkyl, C₁ -C₅ acyl or glycidyl and the esters are prepared from the compound wherein R is hydrogen by means of esterification with a carboxylic acid and a mineral acid catalyst and ethers are prepared from the compound wherein R equals H using a sodium hydride/alkyl iodide compound and the glycidyl ethers are prepared from allyl ethers by treatment with peracids.

A number of the aldehydes found to be useful in our invention are known in the prior art.

Thus, Japanese Pat. No. J76-011625 of April 1976 (assigned to Nado Research Institute Company) discloses a genus of compounds defined according to the structure: ##STR9## wherein R₁ ""' represents hydrogen, alkyl, or one of the moieties: ##STR10## and R₂₁ is hydrogen or alkyl; and wherein Y represents hydrogen, alkyl or one of the moieties: ##STR11## wherein R₃₁ represents hydrogen or alkyl.

In addition, Japanese Pat. No. J75-135071 abstracted at Vol. 84, Chem. Abstracts 43466h discloses the compound having the structure: ##STR12## and Chem. Abstract Vol. 60, 4026g (1964) (Abstract of Compt. Rend. 257 (20) 2995-8 (1963) discloses the compound having the structure: ##STR13##

None of the references disclosing the foregoing tetracyclic carboxaldehydes discloses their utilization for augmenting or enhancing the aroma or taste of consumable materials.

In addition, nothing in the prior art discloses the other compounds of our invention or organoleptic utilities of any mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the reaction product of Example I containing the compound having the structure: ##STR14##

FIG. 2 is the NMR spectrum for the reaction product of Example I containing the compound having the structure: ##STR15##

FIG. 3 is the infra-red spectrum for the reaction product of Example I containing the compound having the structure: ##STR16##

FIG. 4 is the GLC profile for the reaction product of Example II containing the compound having the structure: ##STR17##

FIG. 5 is the NMR spectrum for fraction 11 of the distillation product of the reaction product of Example II containing the compound having the structure: ##STR18##

FIG. 6 is the infra-red spectrum for fraction 11 of the distillation product of the reaction product of Example II containing the compound having the structure: ##STR19##

FIG. 7 is the GLC profile for the reaction product of Example III containing the compound having the structure: ##STR20##

FIG. 8 is the NMR spectrum for Peak 13 of the GLC profile of FIG. 7 for the reaction product of Example III containing the compound having the structure: ##STR21##

FIG. 9 is the GLC profile for bulked fractions 3-11 of the distillation product of the reaction product of Example IV containing the compound having the structure: ##STR22##

FIG. 10 is the NMR spectrum for bulked fractions 3-11 of the distillation product of the reaction product of Example IV containing the compound having the structure: ##STR23##

FIG. 11 is the infra-red spectrum for bulked fractions 3-11 of the distillation product of the reaction product of Example IV containing the compound having the structure: ##STR24##

FIG. 12 is the GLC profile for the reaction product of Example V containing the compound having the structure: ##STR25##

FIG. 13 is the NMR spectrum for fraction 8 of the distillation product of the reaction product of Example V containing the compound having the structure: ##STR26##

FIG. 14 is the infra-red spectrum for fraction 8 of the distillation product of the reaction product of Example V containing the compound having the structure: ##STR27##

FIG. 15 is the GLC profile for the reaction product of Example VI containing the compound having the structure: R1 ? ##STR28##

FIG. 16 is the NMR spectrum for fraction 6 of the distillation product of the reaction product of Example VI containing the compound having the structure: ##STR29##

FIG. 17 is the infra-red spectrum for fraction 6 of the distillation product of the reaction product of Example VI containing the compound having the structure: ##STR30##

FIG. 18 is the GLC profile for the reaction product of Example VII containing the compound having the structure: ##STR31##

FIG. 19 is the NMR spectrum for fraction 9 of the distillation product of the reaction product of Example VII containing the compound having the structure: ##STR32##

FIG. 20 is the infra-red spectrum for fraction 9 of the distillation product of the reaction product of Example VII containing the compound having the structure: ##STR33##

FIG. 21 is the GLC profile for the reaction product of Example VIII containing a mixture of compounds defined according to the structures: ##STR34##

FIG. 22 is the NMR spectrum for Peak 51 of the GLC profile of FIG. 21 for the mixture of compounds defined according to the structures: ##STR35##

FIG. 23 is the infra-red spectrum for Peak 51 of the GLC profile of FIG. 21 for the reaction product of Example VIII containing a mixture of compounds defined according to the structures: ##STR36##

FIG. 24 is the GLC profile for the reaction product of Example IX containing the compound defined according to the structure: ##STR37##

FIG. 25 is the NMR spectrum for the distillation product of the reaction product of Example IX containing the compound having the structure: ##STR38##

FIG. 26 is the infra-red spectrum for the distillation product of the reaction product of Example IX containing the compound having the structure: ##STR39##

FIG. 27 is the GLC profile for the reaction product of Example X containing the compound having the structure: ##STR40##

FIG. 28 is the NMR spectrum for the distillation product of the reaction product of Example X containing the compound having the structure: ##STR41##

FIG. 29 is the infra-red spectrum for the distillation product of the reaction product of Example X containing the compound having the structure: ##STR42##

DETAILED DESCRIPTION OF THE DRAWINGS

FIG. 1 is the GLC profile for the reaction product of Example I containing the compound having the structure: ##STR43## The peak indicated by the reference numeral 1 is the peak for the compound having the structure: ##STR44##

FIG. 7 is the GLC profile for reaction product of Example III. The peak indicated by the reference numeral 11 is for the compound defined according to the structure: ##STR45## The peak indicated by the reference numeral 12 is for the compound defined according to the structure: ##STR46## The peak indicated by the reference numeral 13 is for the reaction product defined according to the structure: ##STR47##

FIG. 9 is the GLC profile for the reaction product of Example IV, bulked distillation fractions 3-11. The peak indicated by the reference numeral 21 is for the reaction product having the structure: ##STR48##

FIG. 12 is the GLC profile for the reaction product of Example V. The peak indicated by the reference numeral 31 is for the reaction product having the structure: ##STR49##

FIG. 15 is the GLC profile for the reaction product of Example VI. The peak indicated by the reference numeral 41 is for the reaction product having the structure: ##STR50##

FIG. 21 is the GLC profile for the reaction product of Example VIII. The peak indicated by the reference numeral 51 is for the reaction product which is a mixture of compounds defined according to the structures: ##STR51##

THE INVENTION

It has now been determined that certain mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives are capable of imparting a variety of flavors and fragrances to various consumable materials.

Briefly, our invention contemplates augmenting or enhancing the flavors and/or fragrances of such consumable materials by adding thereto a small but effective amount of at least one such mono-oxomethyl substituted polyhydrodimethanonaphthalene derivative defined according to the generic structure: ##STR52## wherein the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond; wherein R₁, R₁ ', R₁ ", R₁ '", R₁ "", R₃, R₅, R₅ ', R₅ ", R₅ '", R₅ "" and R₆ represent hydrogen or methyl with the provisos:

(i) at least four of R₁, R₁ ', R₁ ", R₁ '" and R₁ "" are hydrogen and (ii) at least four of R₅, R₅ ', R₅ ", R₅ '" and R₅ "" represent hydrogen; and wherein Z represents one of the moieties:

(i) carboxaldehyde having the structure: ##STR53## (ii) alkylene dioxy or dialkoxy methyl having the structure: ##STR54## (iii) hydroxymethyl having the structure: ##STR55## (iv) acetoxymethyl having the structure: ##STR56## and wherein R₇ and R₈ taken separately represent C₁ -C₄ lower alkyl or R₇ and R₈ taken together represent C₂ -C₄ alkylene; wherein the line represented by:

    [++++]

is either a carbon-carbon single bond when R₇ and R₈ taken together are C₂ -C₄ alkylene or no bond at all when R₇ and R₈ taken separately represent C₁ -C₄ lower alkyl.

Also described are processes for preparing such mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives, and processes for using the above defined mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives for their organoleptic properties and compositions containing said mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives including perfumes, perfumed articles such as solid or liquid anionic, cationic, nonionic or zwitterionic detergents, perfumed polymers, fabric softeners and cosmetic powders; and foodstuffs, chewing gums, toothpastes, medicinal products, chewing tobaccos, smoking tobaccos and smoking tobacco articles; and flavoring compositions (e.g., for foodstuffs, chewing gums, chewing tobaccos, medicinal products, toothpastes and smoking tobaccos) and fragrance compositions (e.g., for perfume compositions and compositions for augmenting or enhancing the aroma of perfumed articles such as solid or liquid anionic, cationic, nonionic or zwitterionic detergents or fabric softeners or fabric softener articles or cosmetic powders or perfumed polymers) containing such mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives.

The mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives produced according to the processes of our invention which are used in practicing that part of our invention concerning flavoring and fragrance compositions are actually racemic mixtures rather than individual optical isomers such as is the case concerning isomers of patchouli alcohol which are obtained from patchouli oil.

The mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention insofar as their fragrance profiles are concerned have intense and long lasting melony, cucumber, violet-like, green, leafy, herbaceous, wormwood-like, floral, cinnamic, sandalwood-like, patchouli-like, vetiver-like, sweaty, animalic and spicy aromas. Insofar as their flavor uses are concerned (e.g., foodstuffs, chewing gums, medicinal products, chewing tobaccos and toothpastes) the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention have sweet, aldehydic, floral, melony, herbaceous, green and artichoke-like aroma and taste profiles.

Insofar as smoking tobacco flavors are concerned the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention have sweet, floral and green aroma profiles prior to smoking and sweet, floral and aramatic aroma and taste nuances on smoking both in the main stream and in the side stream.

                                      TABLE I                                      __________________________________________________________________________     The following table sets forth the structure and organoleptic property         profiles for specific compounds                                                according to the examples listed herein and located infra:                     Structure                           Food        Tobacco                        of                     Fragrance    Flavor      Flavor                         Compound               Profile      Profile     Profile                        __________________________________________________________________________      ##STR57##             A melony, cucumber- like, violet-like, green,                                  herbaceous, wormwood-like, and floral                                                       Sweet, aldehyde, floral, melony and                                            herbaceous aroma at                                                                        A sweet,                                                                       floral, herbaceous aroma                                                       prior to smoking and a                                                         sweet, floral and                                                              aramatic flavor and taste                                                      on smoking in both the                                                         main stream and the side                                                       stream.                         ##STR58##             A floral, fruity (melony) cinnamic aroma.                                                   A sweet, melony, cinnamon-like aroma                                           and taste profile.                                                                          A cinnamon/floral aroma                                                       prior to smoking and                                                           intense cinnamon-like                                                          nuances and aramatic                                                           tobacco notes on smoking                                                       in both the main stream                                                        and the side stream.            ##STR59##             A sandalwood-like- patchouli-like and vetiver-like                             aroma profile.                                                                              A walnut-like aroma and taste                                                  profile.    A nutty/tobacco nuances                                                        proir to smoking and                                                           woody aroma and taste                                                          nuances on smoking in the                                                      main stream and the side                                                       stream.                         ##STR60##             A floral, fruit (pineapple) aroma profile.                                                  An intense pineapple aroma and taste                                           profile.    A sweet, floral, fruity                                                        aroma and taste prior to                                                       smoking and fruity                                                             virginia-like tobacco                                                          notes on smoking in both                                                       the main stream and the                                                        side stream.                    ##STR61##             A sweaty, musk-like aroma profile.                                                          A green, artichoke- like aroma and                                             taste profile.                                                                             --                              ##STR62##             An animalic, leafy, green, herbaceous, floral and                              voilet-like aroma profile with cinnamic and                                    cucumber- like undertones.                                                                  A green, melony, minty, herbaceous                                             and floral aroma and taste profile at                                          2 ppm.      A minty tobacco nuance                                                         prior to smoking and                                                           minty cooling-like notes                                                       on smoking in both the                                                         main stream and the side                                                       stream.                         ##STR63##             A spicy cinnamic-like aroma.                                                                A spicy, cinnamon-like aroma and                                               taste profile.                                                                             A spicy, cinnamon-like                                                         aroma and taste profile                                                        prior to smoking and                                                           spicy turkish oriental-                                                        like tobacco nuances on                                                        smoking in the main                                                            stream and the side                                                            stream.                        __________________________________________________________________________

The mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives produced according to the process of our invention which are used in practicing that part of our invention concerning flavor and fragrance compositions may be mixtures of isomers or they may be substantially pure forms of exo or endo isomers or specific stereoisomers such as in the case concerning isomers of patchouli alcohol which are obtained from patchouli oil.

The mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives prepared according to our invention can be obtained by reacting bicyclopentadiene or dimethyl bicyclopentadiene having the structures: ##STR64## with an acrolein derivative according to the reaction: ##STR65## wherein R₁, R₁ ', R₁ ", R₁ '", R₁ "", R₃, R₅, R₅ ', R₅ ", R₅ '", and R₅ "" are defined, supra. The reaction is carried out at pressures in the range of from about 150 psig up to about 500 psig and at temperatures in the range of from about 150° C. up to about 250° C. in the presence of or in the absence of an inert solvent. When the solvent is used it is preferred to use a solvent such as toluene or xylene which can easily be separated from the reaction mass after the completion of the reaction. The ratio of bicyclopentadiene derivative:acrolein derivative may vary from about 0.5:1 up to about 1:0.5 with the preferred mole ratio being about 1:1. The concentration of reactant in the reaction mass may vary from about 100 grams per liter up to about 500 grams per liter. At the end of the reaction the pressure vessel is opened and the contents are distilled preferably by means of fractional distillation. The reaction product can be used "as is" for its organoleptic properties or it may be further reacted as set forth, infra.

The mechanism for this reaction is as follows: ##STR66## followed by: ##STR67## followed by: ##STR68## wherein R₁, R₁ ', R₁ ", R₁ '", and R₁ "" and R₃, R₅, R₅ ', R₅ " R₅ '", R₅ "" and R₆ are defined, supra.

The resulting aldehyde defined according to the structure: ##STR69## may then be reduced to form the corresponding saturated polycyclic carboxaldehydes or unsaturated polycyclic carboxaldehydes or saturated polycyclic carbinols or unsaturated polycyclic carbinols or the resulting aldehyde may be then reacted with an alkanol or alkanediol to form polycyclic carbinyl acetals, or cyclic acetals. In turn, the resulting carbinols may be acylated as with acetic anhydride or acetyl chloride or acetyl bromide to form the corresponding saturated polycyclic carbinol acetates or unsaturated polycyclic carbinol acetates.

Thus, when reacting the aldehyde derivative defined according to the genus having the structure: ##STR70## with one mole of hydrogen per mole of aldehyde at a pressure in the range of from about 50 psig up to about 200 psig and in the presence of a catalyst such as palladium supported on carbon, palladium supported on barium sulfate, palladium supported on calcium sulfate or palladium supported on calcium carbonate (for example: 5% palladium supported on calcium sulfate, 5% palladium supported on calcium carbonate or 10% palladium on carbon) at a temperature in the range of from about 10° C. up to 140° C., the aldehyde will be reduced to the saturated polycyclic carboxaldehyde according to the reaction: ##STR71##

On the other hand when two moles of hydrogen are used per mole of aldehyde, the reduction is such that a saturated polycyclic carbinol is formed according to the reaction: ##STR72##

The aldehyde genus defined according to the structure: ##STR73## may be reduced with an alkali metal borohydride or lithium aluminum hydride in the presence of an inert solvent to form the unsaturated polycyclic carbinol according to the reaction: ##STR74## wherein M represents alkali metal such as lithium, sodium or potassium.

The reaction is carried out in the presence of an inert solvent such as isopropyl alcohol, n-propyl alcohol, ethyl alcohol or methyl alcohol or diethyl ether or tetrahydrofuran. The reaction is carried out at a temperature in the range of from about 20° C. up to reflux conditions (depending upon the solvent used) and is most conveniently and preferably carried out at atmospheric pressures since higher pressures do not give rise to higher yields or higher conversions. The mole ratio of alkali metal borohydride:aldehyde reactant or lithium aluminum hydride:aldehyde reactant may vary from about 0.2:1 up to about 1:1 with a preferred mole ratio of 0.25:1 up to 0.5:1.

Both the saturated and unsaturated polycyclic carbinols defined according to the structures: ##STR75## may be further reacted as by acetylation using acetic anhydride or acetyl chloride. The reaction with acetic anhydride is preferably carried out in the presence of an inert solvent at reflux conditions at atmospheric pressure. Such an inert solvent is toluene or xylene, the solvents being inert and having boiling points such that the reaction may proceed efficiently and in a minimum amount of time. Preferably the mole ratio of acetic anhydride:carbinol reactant is from about 0.5:1.5 up to about 1.5:0.5 with a most preferred ratio of acetic anhydride:carbinol reactant being 1-1.5:1. Each of these reactions is set forth as follows: ##STR76##

In addition, the aldehyde derivatives defined according to the structure: ##STR77## may be converted into cyclic or acyclic acetals by means of reaction of the aldehyde with a C₁ -C₄ alkanol or a C₂ -C₄ alkanediol according to the reaction: ##STR78## wherein R₁, R₁ ', R₁ ", R₁ '", R₁ "", R₃, R₅, R₅ ', R₅ ", R₅ '", R₅ "", R₆, R₇, R₈ and the line [++++] are defined, supra.

The reaction is carried out in the presence of a protonic acid catalyst or a Lewis acid catalyst at a temperature in the range of from about 30° C. up to about 90° C. Preferred catalysts are boron trifluoride etherate, 20% sulfuric acid, saturated aqueous, ammonium chloride and stannic chloride.

The preferred mole ratio of alkane diol:aldehyde reactant may vary from about 1:1 up to aboue 2:1 and the preferred mole ratio of alkylenediol:aldehyde reactant may vary from about 2:1 up to about 4:1.

At the end of each of the foregoing reactions the reaction product may, if desired, be separated from the resultant reaction mass by fractional distillation or preparative GLC (vapor phase, chromotography). However, if the desired reaction product is to be utilized as a reaction intermediate, the necessity of careful rectification of the reaction product in order to achieve odor acceptable substances or flavor acceptable substances is not usually necessary since the resultant reaction product will be further reacted.

Thus, the individual mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention can be obtained in pure form or in substantially pure form by conventional purification techniques. The products can be purified and/or isolated not only by distillation (as mentioned, supra), but also using extraction, crystallization, preparative chromatographic techniques and the like. It has been found desirable to purify the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention by fractional distillation in vacuo.

When the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention are used as food flavor adjuvants, the nature of the co-ingredients included with said mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives in formulating the product composition will also serve to alter, modify, augment or enhance the organoleptic characteristics of the ultimate foodstuff treated therewith.

As used herein in regard to flavors, the terms "alter", "modify" and "augment" in their various forms mean "supplying or imparting flavor character or note to otherwise bland, relatively tasteless substances or augmenting the existing flavor characteristic where a natural flavor is deficient in some regard or supplementing the existing flavor impression to modify its quality, character or taste."

The term "enhance" is used herein to mean the intensification of a flavor or aroma characteristic or note without the modification of the quality thereof. Thus, "enhancement" of a flavor or aroma means that the enhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquid ingestible materials which usually do, but need not, have nutritional value. Thus, foodstuffs include soups, convenience foods, beverages, dairy products, candies, vegetables, cereals, soft drinks, snacks and the like.

As used herein, the term "medicinal product" includes both solids and liquids which are ingestible, non-toxic materials which have medicinal value such as cough syrups, cough drops, aspirin and chewable medicinal tablets.

The term "chewing gum" is intended to mean a composition which comprises a substantially water insoluble, chewable, plastic gum base such as chicle, or substitutes therefor, including guttakay rubber or certain comestible natural or synthetic resins or waxes. Incorporated with the gum base in admixture therewith may be plasticizers or softening agents, e.g., glycerine, and a flavoring composition which incorporates one or more of the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention, and in addition, sweetening agents which may be sugars, including sucrose or dextrose and/or artificial sweeteners such as cyclamates or saccharin. Other optional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoring adjuvants are well known in the art for such use, being extensively described in the relevant literature. It is a requirement that any such material be "ingestibly" acceptable and thus non-toxic and otherwise non-deleterious particularly from an organoleptic standpoint whereby the ultimate flavor and/or aroma of the consumable material used is not caused to have unacceptable aroma and taste nuances. Such materials may in general be characterized as flavoring adjuvants or vehicles comprising, broadly, stablizers, thickeners, surface active agents, conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride; antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid, butylated hydroxyanisole (mixture of 2- and 3-tertiary-butyl-4-hydroxy-anisole), butylated hydroxytoluene (2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like, and sequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids, suspending agents, emulsifiers and the like, e.g., agar agar, carrageenan; cellulose and cellulose derivatives such as carboxymethyl cellulose and methyl cellulose; natural and synthetic gums such as gum arabic, gum tragacanth; gelatin, proteinaceous materials; lipids, carbohydrates; starches, pectins, and emulsifiers, e.g., mono- and diglycerides of fatty acids, skim milk powder, hexoses, pentoses, disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids such as capric acid, caprylic acid, palmitic acid, myristic acid and the like, mono- and diglycerides of fatty acids, lecithin, defoaming and flavor-dispersing agents such as sorbitan monostearate, potassium stearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents, e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and the like; starch modifiers such as peracetic acid, sodium chlorite, sodium hypochlorite, propylene oxide, succinic anhydride and the like, buffers and neutralizing agents, e.g., sodium acetate, ammonium bicarbonate, ammonium phosphate, citric acid, lactic acid, vinegar and the like; colorants, e.g., carminic acid, cochineal, tumeric and curcuma and the like; firming agents such as aluminum sodium sulfate, calcium chloride and calcium gluconate; texturizers, anti-caking agents, e.g., aluminum calcium sulfate and tribasic calcium phosphate; enzymes; yeast foods, e.g., calcium lactate and calcium sulfate; nitrient supplements, e.g., iron salts such as ferric phosphate, ferrous gluconate and the like, riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfate and the like.

Other flavorants and flavor intensifiers include organic acids, e.g., acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid, caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovaleric acid, alpha-methylbutyric acid, propionic acid, valeric acid, 2-methyl-2-pentenoic acid, and 2-methyl-3-pentenoic acid; ketones and aldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methyl carbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methylbutanal, beta-beta-dimethylacrolein, methyl n-amyl ketone, n-hexanal, 2-hexenal, isopentanal, hydrocinnamic aldehyde, cis-3-hexenal, 2-heptenal, nonyl aldehyde, 4-(p-hydroxyphenyl)-2-butanone, alpha-ionone, beta-ionone, 2-methyl-3-butanone, benzaldehyde, β-damascone, α-damascone, β-damascenone, acetophenone, 2-heptanone, o-hydroxyacetophenone, 2-methyl-2-hepten-6-one, 2-octanone, 2-undecanone, 3-phenyl-4-pentenal, 2-phenyl-2-hexenal, 2-phenyl-2-pentenal, furfural, 5-methyl-furfural, cinnamaldehyde, beta-cyclohomocitral, 2-pentanone, 2-pentenal and propanal; alcohols such as 1-butanol, benzyl alcohol, 1-borneol, trans-2-buten-1-ol, ethanol, geraniol, 1-hexanol, 2-heptanol, trans-2-hexenol-1, cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentanol, 1-penten- 3-ol, p-hydroxyphenyl-2-ethanol, isoamyl alcohol, isofenchyl alcohol, phenyl-2-ethanol, alpha-terpineol, cis-terpin hydrate, eugenol, linalool, 2-heptanol, acetoin; esters, such as butyl acetate, ethyl acetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethyl caprate, ethyl caproate, ethyl carpylate, ethyl cinnamate, ethyl crotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyl laurate, ethyl myristate, ethyl α-methylbutyrate, ethyl propionate, ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenyl butyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methyl acetate, methyl butyrate, methyl caproate, methyl isobutyrate, alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate, cinnamyl formate, methyl cinnamate and terpenyl acetate; hydrocarbons such as dimethyl naphthalene, dodecane, methyldiphenyl, methyl naphthalene, myrcene, naphthalene, octadecane, tetradecane, tetramethylnaphthalene, tridecane, trimethylnaphthalene, undecane, caryophyllene, α-phellandrene, β-phellandrene, p-cymene 1-α-pinene, beta-pinene, dihydrocarveol; pyrazines such as 2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine, 3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine, 3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3-dimethylpyrazine, 2-isoamyl-3,5,6-trimethylpyrazine, isopropyl dimethylpyrazine, methyl ethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oils such as jasmine absolute, cassia oil, cinnamon bark oil, black pepper oleoresin, oil of black pepper, rose absolute, orris absolute, oil of cubeb, oil of coriander, oil of pimento leaf, oil of patchouli, oil of nutmeg, lemon essential oil, safran oil, Bulgarian rose, capsicum, yara yara and vanilla; lactones such as γ-nonalactone; Δ-decalactone; γ&Δ-undecalactone; γ&Δ-dodecalactone; sulfides, e.g., methyl sulfide and other materials such as maltol, and acetals (e.g., 1,1-diethoxyethane, 1-1-dimethoxyethane and dimethoxymethane), piperine, chavicine, and piperidine.

The specific flavoring adjuvant selected for use may be either solid or liquid depending upon the desired physical form of the ultimate product, i.e., foodstuff, whether simulated or natural, and should, in any event, (i) be organoleptically compatible with the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention by not covering or spoiling the organoleptic properties (aroma and/or taste thereof); (ii) be non-reactive with the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention; and (iii) be capable of providing an environment in which the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention can be dispersed or admixed to provide a homogeneous medium. In addition, selection of one or more flavoring adjuvants, as well as the quantities thereof will depend upon the precise organoleptic character desired in the finished product. Thus, in the case of flavoring compositions, ingredient selection will vary in accordance with the foodstuff, chewing gum, medicinal product or toothpaste to which the flavor and/or aroma are to be imparted, modified, altered or enhanced. In contradistinction, in the preparation of solid products, e.g., simulated foodstuffs, ingredients capable of providing normally solid compositions should be selected such as various cellulose derivatives.

As will be appreciated by those skilled in the art, the amount of mono-oxomethyl substituted polyhydrodimethanonaphthalene derivative(s) of our invention employed in a particular instance can vary over a relatively wide range, depending upon the desired organoleptic effects to be achieved. Thus, correspondingly greater amounts would be necessary in those instances wherein the ultimate food composition to be flavored (e.g., with a peppermint flavor, or a specific vegetable flavor such as an artichoke flavor) is relatively bland to the taste, whereas relatively minor quantities may suffice for purposes of enhancing a composition merely deficient in natural flavor or aroma. The primary requirement is that the amount selected be effective, i.e., sufficient to alter, modify or enhance the organoleptic characteristics of the parent composition, whether foodstuff per se, chewing gum per se, medicinal product per se, toothpaste per se, of flavoring composition.

The use of insufficient quantities of mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention will, of course, substantially vitiate any possibility of obtaining the desired results while excess quantities prove needlessly costly and in extreme cases may disrupt the flavor-aroma balance, thus proving self-defeating. Accordingly, the terminology "effective amount" and "sufficient amount" is to be accorded a significance in the context of the present invention consistent with the obtention of desired flavoring effects.

Thus, and with respect to ultimate food compositions, chewing gum compositions, medicinal product compositions and toothpaste compositions, it is found that quantities of mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention ranging from a small but effective amount, e.g., 0.00001 parts per million up to about 100 parts per million based on total composition, are suitable. Concentrations in excess of the maximum quantity stated are not normally recommended since they fail to provide commensurate enhancement of organoleptic properties. In those instances wherein the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention are added to the foodstuff as an integral component of a flavoring composition, it is of course essential that the total quantity of flavoring composition employed be sufficient to yield an effective mono-oxomethyl substituted polyhydrodimethanonaphthalene derivative concentration in the foodstuff product.

Food flavoring compositions prepared in accordance with the present invention preferably contain the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention in concentrations ranging from about 0.01% up to about 15% by weight based on the total weight of the said flavoring composition.

The composition described herein can be prepared according to conventional techniques well known as typified by cake batters and fruit drinks and can be formulated by merely admixing the involved ingredients within the proportions stated in a suitable blender to obtain the desired consistency, homogeneity of dispersion, etc. Alternatively, flavoring compositions in the form of particulate solids can be conveniently prepared by mixing the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention with, for example, gum arabic, gum tragacanth, carrageenan, xanthangum, guargum, mixtures of same and the like, and thereafter spray-drying the resultant mixture whereby to obtain the particular solid product. Prepared flavor mixes in powder form, e.g., a fruit flavored powder mix, are obtained by mixing the dried solid components, e.g., starch, sugar and the like, and one or more mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention in a dry blender until the requisite degree of uniformity is achieved.

It is presently preferred to combine with the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention, the following adjuvants:

Oil of Cubeb;

α-phellandrene;

β-phellandrene;

Oil of Coriander;

Oil of Pimento Leaf;

Oil of Patchouli;

Alpha Pinene;

Beta Pinene;

Beta-caryophyllene;

Dihydrocarveol;

Piperonal;

Piperine;

Chavicine;

Piperidine;

Oil of Black Pepper;

Black Pepper Oleoresin;

Capsicum;

Oil of Nutmeg;

Cardamom Oil;

Clove Oil;

Spearment Oil;

Oil of Peppermint;

Ethyl-2-methyl butyrate;

Vanillin;

Butyl valerate;

2,3-Diethyl pyrazine;

Methyl cyclopentenolone;

Benzaldehyde;

Valerian Oil Indian;

Propylene glycol;

Aetaldehyde;

Isobutyraldehyde;

Isovaleraldehyde;

Dimethyl sulfide;

Isobutyl acetate;

Isoamyl acetate;

Phenylethyl acetate;

Diacetyl;

Acetophenone;

Furfural

Phenylacetaldehyde

Isoamyl alcohol;

β-Phenylethyl alcohol;

α-Phenyl ethyl alcohol

γ-Butyrolactone;

y-Butyrolactone;

3-Phenyl-4-pentenal;

3-Phenyl-3-pentenal;

3-Phenyl-2-pentenal;

2-Methyl pyrazine;

2,6-Dimethyl pyrazine;

2,3,5,6-Tetramethyl pyrazine;

2,3,5-Trimethylpyrazine;

2-Ethyl-3-methylpyrazine;

2-Ethyl-3,5-dimethylpyrazine;

2-Ethyl-3,6-dimethylpyrazine;

2-Ethyl-5-methylpyrazine;

2(n-pentyl) thiazole;

2(i-butyl) thiazole;

2(i-propyl) thiazole;

2(n-propyl) thiazole;

2-phenyl-4-pentenal;

2-phenyl-4-pentenaldimethylacetal;

Methional;

4-methylthiobutanal;

2-ethyl-3-acetylpyrazine

trans-2-hexenal;

Hydrolyzed vegetable protein;

Monosodium glutamate;

Celery Oil;

Lemon Oil;

Mustard Oil;

2,4-dimethyl-Δ³ -thiazoline;

4,5-dimethyl-Δ³ -thiazoline;

2,4,5-trimethyl-Δ³ -thiazoline;

2-propyl-2,4,5-trimethyl-Δ³ -thiazoline;

2-ethyl-2,4,5-trimethyl-Δ³ -thiazoline;

2-(2'butyl)-4-methyl-Δ³ -thiazoline;

2-n-butyl-4,5-dimethyl-Δ³ thiazoline;

2-benzeyl-4-methyl-Δ³ -thiazoline;

2,5-dimethyl-2-benzyl-Δ³ -thiazoline;

2-(2'-methyl-n-propyl)-4.5-dimethyl-Δ³ thiazoline;

β-Damascone

β-Damascenone; and

trans,transΔ³ -Damascone

The mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention can be used to contribute melony, cucumber, violet-like, green, leafy, herbaceous, wormwood-like, floral, cinnamic, sandalwood-like, patchouli-like, vetiver-like, sweaty, animalic and spicy aroma nuances to perfume compositions, perfumed articles (such as solid or liquid anionic, cationic, nonionic or zwetterionic detergents, fabric softeners, fabric softener articles and perfumed polymers) and colognes. As olfactory agents the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention can be formulated into or used as components of a "perfume composition".

The term "perfume composition" is used herein to mean a mixture of organic compounds including, for example, alcohols (other than the alcohols of our invention), aldehydes (other than the aldehydes of our invention), ketones, nitriles, ethers, lactones, acetals (other than the acetals of our invention), esters (other than the esters of our invention), and frequently hydrocarbons which are admixed so that the combined odors of the individual components produce a pleasant or desired fragrance. Such perfume compositions usually contain: (a) the main note or the "bouquet" or foundation-stone of the composition; (b) modifiers which round-off and accompany the main note; (c) fixatives which include odorous substances which lend a particular note to the perfume throughout all stages of evaporation, and substances which retard evaporation; and (d) top-notes which are usually low-boiling, fresh-smelling materials.

In perfume compositions the individual component will contribute its particular olfactory characteristics, but the overall effect of the perfume composition will be the sum of the effects of each ingredient. Thus, the individual compounds of this invention, or mixtures thereof, can be used to alter the aroma characteristics of a perfume composition, for example, by highlighting or moderating the olfactory reaction contributed by another ingredient in the composition.

The amount of the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention which will be effective in perfume compositions depends on many factors, including the other ingredients, their amounts and the effects which are desired. It has been found that perfume compositions containing as little as 0.2% of one or more of the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention, or even less, can be used to impart melony, cucumber-like, violet-like, green, leafy, herbaceous, wormwood-like, floral, cinnamic, sandalwood-like, patchouli-like, vetiver-like, sweaty, animalic, and spicy aroma nuances to soaps, cosmetics, solid or liquid anionic, cationic, nonionic, or zwitterionic detergents, fabric softeners, fabric softener articles, perfumed polymers, cosmetic powders, hair preparations and other products. The amount employed can range up to 50% or higher and will depend on considerations of cost, nature of the end product, the effect desired on the finished product and a particular fragrance sought.

The mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention can be used alone or in a perfume composition as an olfactory component in solid or liquid anionic, cationic, nonionic or zwitterionic detergents, fabric softeners, and soaps; space odorants and deodorants; perfumes; colognes, toilet waters; bath salts; hair preparations such as lacquers, brilliantines, pomades, and shampoos; cosmetic preparations such as creams, deodorants, hand lotions, and sun screens; powders such as talcs, dusting powders, face powder and the like. When used as an olfactory component of a perfumed article, as little as 0.005% of one or more of the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention will suffice to impart an interesting melony, cucumber, violet-like, green, leafy, herbaceous, wormwood-like, floral, cinnamic, sandalwood-like, patchouli-like, vetiver-like, sweaty, animalic and spicy aromas. Generally, no more than 0.8% is required in the perfumed article. Thus, to be specific, the range of mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention useful in perfumed articles varies from about 0.005% up to about 0.8%.

In addition, the perfume composition of our invention can contain a vehicle or carrier for the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention. The vehicle can be a liquid such as an alcohol such as ethanol, a glycol such as propylene glycol, or the like. The carrier can be an absorbent solid such as a gum or components for encapsulating the composition by coacervation such as gelatin or for encapsulating the composition by forming polymers around a central liquid core such as a urea formaldehyde capsule.

It is the further object of our invention to provide a smoking tobacco product treated with an additive which will enhance the tobacco aroma, as well as the flavor characteristics of the tobacco product made therefrom. Also, it is an object of the present invention to provide a smoking tobacco product having a material added to the tobacco which will readily transfer to the tobacco smoke and pass through a filter element (even of a high filtration type) so that the natural flavor qualities of the tobacco smoke are enhanced.

Another object of our invention is the provision of smoking tobacco products, such as cigarettes, cigars, pipe tobacco, or tobacco smoke filters, having added thereto a releasable flavor additive which will impart a desirable fresh natural taste to the smoking product when smoked.

Thus, in general, our invention further contemplates providing an organoleptically improved tobacco product having added thereto one or more mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention which imparts to the product the enhanced and desirable fresh flavor and aroma of natural tobacco. The mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention are individually and in combination readily transferred either from the filter section or the tobacco section into the smoke stream when the tobacco product is smoked. The organoleptic qualities of the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention particularly when transferred to the tobacco smoke, impart desirable fresh, oriental, spicy, floral, citrusy flavor and aroma nuances to tobacco causing the tobacco to be more desirable and causing a change from the "Virginia" and "Burley" types to the "imported", "Turkish" types.

The mono-oxomethyl substituted polyhydrodimethanonaphthalene of our invention employed to improve the organoleptic qualities of a tobacco product have odor characteristics which can be described as floral, spicy, woody, and cinnamon-like as well as citrusy. The amount of mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention taken alone or in combination added to a tobacco product may vary greatly; however a sufficient amount should be used to achieve the desired organoleptic properties for the smoking tobacco product when smoked. We have found that the levels of the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention (taken alone or in combination) added to a tobacco product, either to the filter or to the tobacco section, may be as low as 0.001% based on the weight of the tobacco. The amount of the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives added to the tobacco product may be from about 0.001% up to about 0.1% based on the weight of the tobacco, preferably from about 0.005% up to about 0.05%, and more preferably from about 0.01% up to about 0.015%.

The mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention may be incorporated at any step into the treatment of the tobacco but it is preferred that they be added either separately or in admixture after the tobacco has been cured, aged and shredded and just prior to the manufacture of the desired tobacco product, for example, cigarettes, cigars, pipe tobacco, or other smoking products. Also, it may be added to tobacco smoke filter material prior to forming the filter rod. The additive is conveniently dissolved in a solvent, such as ethyl alcohol, and applied to the tobacco by spraying, dipping or other methods of application generally employed for treating tobacco. Also, it may be sprayed onto the filter material. Although solutions of this compound are preferred, suspensions thereof may be utilized. Other suitable solvents are, for example, acetone, diethyl ether, n-hexane, or the like. After treatment of the tobacco or the filter with at least one of the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention, substantially all of the solvent is evaporated therefrom prior to its manufacture into tobacco products.

The term "tobacco" will be understood herein to mean the natural products such as, for example, Burley, Turkish tobacco, Maryland tobacco, flue-cured tobacco and the like including tobacco-like or tobacco-based products such as reconstituted or homogenized leaf and the like, as well as tobacco substitutes intended to replace natural tobacco, such as lettuce and cabbage leaves and the like. The tobaccos and tobacco products in which the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention are useful include those designed or used for smoking such as in cigarette, cigar and pipe tobacco, as well as products such as snuff, chewing tobacco, and the like.

The following examples I-X are given to illustrate methods for producing the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention. The examples following Example X are given to illustrate embodiments of the utilization of the mono-oxomethyl substituted polyhydrodimethanonaphthalene derivatives of our invention. It will be understood that these examples are illustrative and that the invention is not to be considered as restrictive to these examples except as indicated in the appended claims.

EXAMPLE I PREPARATION OF 1,2,3,4,4A,5,5A,8 OCTAHYDRO-1,4:5,8 DIMETHANONAPHTHALENE-2-CARBOXALDEHYDE ##STR79##

Into a high pressure autoclave are placed the following ingredients:

396 dicyclopentadiene;

252 grams acrolein; and

500 ml toluene

The autoclave is sealed, and with stirring, heated at 225° C. at 200 psig for a period of three hours. At the end of the reaction, the autoclave is opened and a portion of the product is distilled in a "Rushover" apparatus yielding the following fractions:

    ______________________________________                                                 Vapor    Liquid   Vacuum Weight of                                     Fraction                                                                               Temp.    Temp.    mm.Hg. Fractions                                     No.     (°C.)                                                                            (°C.)                                                                            Pressure                                                                              (mg)                                          ______________________________________                                         1       23/50    23/70    50/52  911.0                                         2        56       77      50     802.0                                         3        68      100      40     1031.0                                        4        75      100      30     902.0                                         5        83      115      15     200.0                                         6        86      128      15     125.1                                         7       100      133      10     91.6                                          8       108      137      10     105.5                                         9       120      143       8     96.0                                          10      125      147       8     96.5                                          11      135      168       2                                                                                              1588.0                              12      139      186       2                                                   13      156      220       2     339.0                                         ______________________________________                                    

Fractions 11 and 12 of this distillation are bulked and the resulting bulked fractions are distilled on a fractionaction column yielding the following fractions:

    ______________________________________                                                 Vapor   Liquid   Vacuum        Weight of                               Fraction                                                                               Temp.   Temp.    mm. Hg.                                                                               Reflux Fractions                               No.     (°C.)                                                                           (°C.)                                                                            Pressure                                                                              Ratio  (mg)                                    ______________________________________                                         1       23/77   23/122   2/2    9:1    20.8                                    2       78      125      2      9:1    17.3                                    3       78      126      2      9:1    18.9                                    4       78      125      2      9:1    21.3                                    5       79      126      2      9:1    27.8                                    6       80      127      2      9:1    23.5                                    7       80      128      2      9:1    106.5                                   8       80      127      2      9:1    122.4                                   9       80      129      2      9:1    44.0                                    10      80      129      2      9:1    31.1                                    ______________________________________                                    

    ______________________________________                                                 Vapor   Liquid   Vacuum        Weight of                               Fraction                                                                               Temp.   Temp.    mm. Hg.                                                                               Reflux Fractions                               No.     (°C.)                                                                           (°C.)                                                                            Pressure                                                                              Ratio  (mg)                                    ______________________________________                                         11      83      130      2      9:1    39.0                                    12      83      130      2      9:1    42.4                                    13      83      130      2      1:1    106.4                                   14      83      130      2      1:1    102.3                                   15      83      130      2      1:1    106.9                                   16      83      133      2      1:1    128.1                                   17      83      134      2      1:1    130.1                                   18      84      136      2      1:1    128.7                                   19      86      170      2      1:1    132.0                                   20      78      187      2      1:1    64.2                                    21      50      220      2      1:1    44.1                                    ______________________________________                                    

Fractions 14-19 are bulked and have an herbal, strong, green, aldehydic, wormwood-like, floral aroma profile. Bulked fractions 4-14 has a melony, cucumber-like, violet, green, aldehydic aroma profile.

From a flavor standpoint fraction 14 has a sweet, aldehydic, floral, melony, herbaceous aroma and taste profile at 0.0001 ppm. In addition, it is an excellent vanilla flavor enhancer and orange oil flavor enhancer.

FIG. 1 is the GLC profile of the reaction production prior to distillation (conditions: SE-30 packed column, programmed at 220° C. isothermal (1/4"×10 feet). The peak indicated on FIG. 1 by the reference "1" is for the reaction product having the structure: ##STR80##

FIG. 2 is the NMR spectrum for the bulked fractions 4-20 of the foregoing distillation product containing the compound having the structure: ##STR81##

FIG. 3 is the infra-red spectrum for bulked fractions 4-20 of the foregoing distillation product containing the compound having the structure: ##STR82##

EXAMPLE II PREPARATION OF DECAHYDRO-1,4:5,8 DIMETHANONAPHTHALENE-2-CARBOXALDEHYDE ##STR83##

Into a Parr shaker apparatus is placed the following ingredients:

    ______________________________________                                         Ingredients          Parts by Weight                                           ______________________________________                                          ##STR84##           260 grams (1.3 moles)                                     1% Palladium on carbon                                                                               3 grams                                                  Anhydrous isopropyl alcohol                                                                          80 ml                                                    ______________________________________                                    

The Parr shaker is pressurized with hydrogen to a pressure of between 87 and 109 psig while maintaining the reaction temperature at 48°-54° C. for a period of 14 hours. At the end of this period, the Parr shaker is depressurized, opened and the contents are filtered. The resulting product is then distilled on a fractionation column yielding the following fractions:

    ______________________________________                                                   Vapor   Liquid    Vacuum Weight of                                   Fraction  Temp.   Temp.     mm. Hg.                                                                               Fraction                                    No.       (°C.)                                                                           (°C.)                                                                             Pressure                                                                              (gm)                                        ______________________________________                                         1          35      37       20/20  13.6                                        2         119     120       1      10.6                                        3         122     122       1      15.6                                        4         127     127       1      15.1                                        5         127     140       1      16.7                                        6         127     140       1      16.7                                        7         127     140       1      18.1                                        8         127     140       1      19.5                                        9         127     140       1      16.0                                        10        127     140       1      15.6                                        11        127     147       1      17.3                                        12        127     147       1      21.2                                        13        127     147       1      22.5                                        14        130     200       1      22.7                                        ______________________________________                                    

Fraction 7-13 of the foregoing distillation are bulked for subsequent evaluation and for subsequent reaction. Fractions 7-13, bulked, from a fragrance standpoint, have a floral, cinnamon-like and melony aroma profile.

FIG. 4 is the GLC profile for the reaction product prior to distillation. (Conditions: SE-30 column programmed at 130°-220° C. at 8° C. per minute).

FIG. 5 is the NMR spectrum for fraction 11 of the foregoing distillation containing the compound having the structure: ##STR85##

FIG. 6 is the infra-red spectrum for fraction 11 of the foregoing distillation containing the compound having the structure: ##STR86##

EXAMPLE III PREPARATION OF DIMETHYL ACETAL OF 1,2,3,4,4A,5,5A,8 OCTAHYDRO-1,4:5,8 DIMETHANONAPHTHALENE-2-CARBOXALDEHYDE ##STR87##

Into a 100 ml reaction flask equipped with stirrer, thermometer, reflux condenser and heating mantle is placed the following:

10.0 grams of the reaction product of Example I, bulked fractions 22-26 containing the compound having the structure: ##STR88## 4.0 grams borontrifluoride etherate 25.0 grams anhydrous methyl alcohol

The reaction mass is heated to 60° C. and maintained at 60° C. for a period of three hours.

The reaction product having the structure: ##STR89## (as confirmed by NMR, IR mass spectral analyses) is trapped via preparative GLC. (Conditions: SE-30 column programmed at 220° C., isothermal)

FIG. 7 is the GLC profile for the reaction product of this example. The peak indicated by the reference "11" is the peak for the staring material, the aldehyde having the structure: ##STR90## The peak indicated by the reference numeral "12" is for a side-product having the structure: ##STR91## The peak indicated by the reference numeral "13" is the peak for the reaction product having the structure: ##STR92##

FIG. 8 is the NMR spectrum for the peak "13" of the GLC profile of FIG. 7.

EXAMPLE IV PREPARATION OF 1,2,3,4,4A,5,8,8A-OCTAHYDRO 1,4:5,8-DIMETHANONAPHTHALENE-2-METHANOL ##STR93##

Into a 1 liter reaction flask equipped with stirrer, thermometer, reflux condenser and heating mantle is placed 500 grams of isopropyl alcohol and 60 grams of sodium borohydride. The resulting mixture is heated to 50° C. While maintaining this mixture at 50° C., over a period of one hour 300 grams of the aldehyde produced according to Example I, bulked fractions 22-26 having the structure: ##STR94## is added to the reaction mass. The reaction mass is then maintained at 60° C. for a period of 0.5 hours.

The reaction mass is then cooled and washed with 2 liters of water. An aqueous 10% solution of hydrochloric acid is then added until the solution is clear. The reaction mass is then washed and neutralized with sodium carbonate.

The reaction mass is then distilled on a 1"×12" Goodloe column yielding the following fractions:

    ______________________________________                                                                                Weight                                         Vapor     Liquid   Vacuum       of                                      Fraction                                                                              Temp.     Temp.    mm. Hg.                                                                               Ratio Fraction                                No.    (°C.)                                                                             (°C.)                                                                            Pressure                                                                              Reflux                                                                               (gm)                                    ______________________________________                                         1       23/110    27/147  1/1    9:1   14.0                                    2      111       147      0.8    9:1   15.3                                    3      111       147      0.65   9:1   20.1                                    4      111       147      0.65   9:1   24.3                                    5      116       153      0.65   1:1   26.1                                    6      122       157      0.65   1:1   27.1                                    7      122       158      0.65   1:1   25.0                                    8      122       161      0.65   1:1   27.4                                    9      121       168      0.65   1:1   26.3                                    10     119       196      0.65   1:1   25.8                                    11     115       230      0.65   1:1   17.6                                    12     100       235      --     --    --                                      ______________________________________                                    

Bulked fraction 6-10 of the foregoing distillation have a sandalwood-like, patchouli-like and vetiver-like aroma profile.

FIG. 9 is the GLC profile for bulked fractions 3-11 of of the distillation product of the foregoing reaction product. The peak indicated by the reference numeral "21" is the peak indicating the product having the structure: ##STR95## The conditions for the GLC operation are: SE-30 column operated at 220° C. isothermal.

FIG. 10 is the NMR spectrum for bulked fractions 3-11 of foregoing distillation containing the compound having the structure: ##STR96##

FIG. 11 is the infra-red spectrum for bulked fractions 3-11 of the foregoing distillation containing the compound having the structure: ##STR97##

EXAMPLE V PREPARATION OF 1,4:5,8-DIMETHANONAPHTHALENE-2-METHANOL DECAHYDRO ##STR98##

Into a 1 liter reaction vessel equipped with reflux condenser, thermometer, addition funnel, heating mantle and stirrer is placed 500 grams of isopropyl alcohol and 40 grams of sodium borohydride. Over a period of 20 minutes, 280 grams (1.3 moles) of bulked fractions 4-11 of the distillation product of Example II containing the compound having the structure: ##STR99## is added to the reaction mass, with refluxing. The reaction mass is maintained at a temperature of 70°-80° C. for a period of 20 hours.

At the end of the 20 hour period 200 ml acetone is added to the reaction mass. Then, 1.5 liters of water is added to the reaction mass and the aqueous phase is separated from the organic phase. The organic phase crystallizes, at room temperature. The organic phase is distilled on a fractionation column yielding the following fractions:

    ______________________________________                                                   Vapor       Liquid  Weight of                                        Fraction  Temp.       Temp.   Fraction                                         No.       (°C.)                                                                               (°C.)                                                                           (gm)                                             ______________________________________                                         1         130         140     16.1                                             2         130         140     21.5                                             3         130         140     17.3                                             4         130         140     22.7                                             5         130         140     20.0                                             6         130         140     29.9                                             7         130         147     28.4                                             8         130         220     23.0                                             ______________________________________                                    

FIG. 12 is the GLC profile for the reaction product prior to distillation. The peak indicated by the reference numeral "31" is for the reaction product, the compund having the structure: ##STR100## (Conditions: SE-30 column operated at 220° C. isothermal).

FIG. 13 is the NMR spectrum for fraction 8 of the foregoing distillation containing the compound having the structure: ##STR101##

FIG. 14 is the infra-red spectrum for fraction 8 of the foregoing distillation containing the compound having the structure: ##STR102##

EXAMPLE VI PREPARATION OF 1,4:5,8-DIMETHANONAPHTHALENE-2-METHANOL-DECAHYDRO ACETATE ##STR103##

Into a 1 liter reaction flask equipped with stirrer, thermometer, and reflux condenser is placed 160.0 grams of acetic anhydride, 200.0 ml toluene and 178.9 grams of the alcohol reaction product produced according to Example V, bulked fractions 3-8 having the structure: ##STR104## The reaction mass is heated to 116° C. and maintained at 116° C. for a period of 2 hours. At the end of the reaction, 1 liter of water is added to the reaction mass and the organic phase is separated from the aqueous phase. The organic phase is washed with saturated sodium carbonate and the resulting product is fractionally distilled yielding the following fractions:

    ______________________________________                                                   Vapor   Liquid    Vacuum Weight of                                   Fraction  Temp.   Temp.     mm. Hg.                                                                               Fraction                                    No.       (°C.)                                                                           (°C.)                                                                             Pressure                                                                              (gm)                                        ______________________________________                                         2         147     152       2      19.4                                        3         137     150       1      14.1                                        4         135     140       1      14.1                                        5         120     130       1      17.2                                        6         117     135       1      21.0                                        7         117     140       1      24.3                                        8         120     140       1      18.5                                        9         127     148       1      15.8                                        10        128     152       1      23.0                                        11        131     163       1      10.9                                        12        134     270       1      11.9                                        ______________________________________                                    

Fraction 8-10 are bulked for subsequent evaluation. Fractions 8-10 have a floral, pineapple-like aroma from a perfumery standpoint and a pineapple taste.

FIG. 15 is the GLC profile for the reaction product prior to distillation (Conditions: SE-30 column, programmed at 220° C. isothermal). The peak indicated by the reference numeral "41" is the peak for the reaction product having the structure: ##STR105##

FIG. 16 is the NMR spectrum for fraction 6 of the foregoing distillation containing the compound having the structure: ##STR106##

FIG. 17 is the infra-red spectrum for fraction 6 of the foregoing distillation containing the compound having the structure: ##STR107##

EXAMPLE VII PREPARATION OF 1,2,3,4,4A,5,8,8A-OCTAHYDRO-1,4:5,8-DIMETHANONAPHTHALENE-2-METHANOL ACETATE ##STR108##

Into a 1 liter reaction flask equipped with stirrer, thermometer and reflux condenser are placed 102 grams of acetic anhydride, 500.0 ml toluene and 72.0 grams of the alcohol reaction product produced according to Example IV, bulked fractions 6-10 having the structure: ##STR109## The reaction mass is heated to 117° C. and maintained at 117° C. for a period of 1.5 hours. At the end of the reaction, the toluene solvent is stripped and the reaction mass is washed with concentrated aqueous sodium carbonate. The reaction mass is then distilled on a fractionation column yielding the following fractions:

    ______________________________________                                                   Vapor       Liquid  Weight of                                        Fraction  Temp.       Temp.   Fraction                                         No.       (°C.)                                                                               (°C.)                                                                           (gm)                                             ______________________________________                                         1         126         180     1.9                                              2         128         190     6.2                                              3         130         195     4.7                                              4         130         200     9.2                                              5         130         205     3.5                                              ______________________________________                                    

Fractions 2-4 are bulked. The bulked fractions from a perfumery standpoint have a sweaty aroma nuance. From a flavor standpoint, bulked fractions 2-4 at a concentration of 1 ppm have a green, artichoke-like aroma and taste profile making it useful for augmenting or enhancing the aroma and taste of salad dressings.

FIG. 18 is the GLC profile of the reaction product of this example containing the compound having the structure: ##STR110##

FIG. 19 is the NMR spectrum for fraction 4 of the foregoing distillation containing the compound having the structure: ##STR111##

FIG. 20 is the infra-red spectrum for fraction 4 of the foregoing distillation product containing the compound having the structure: ##STR112##

EXAMPLE VIII PREPARATION OF DIMETHYL 1,2,3,4,4A,5,8,8A-OCTAHYDRO-1,4:5,8-DIMETHANONAPHTHALENE-2-CARBOXALDEHYDE ##STR113##

Into a 2 liter autoclave is placed the following materials:

(a) 400 grams of methyl cyclopentadiene dimer, a mixture of compounds defined according to the structures: ##STR114## (b) 200 grams acrolein; and (c) 300 ml toluene.

The autoclave is sealed and heated to 225° C. (180 psig) and maintained at that temperature and pressure for a period of two hours. At the end of the two hour period, the autoclave is depressurized and opened. The reaction product is analyzed via GLC, NMR, IR and mass spectral analyses. The resulting product has an animalic, leafy, green, herbaceous, floral (violet-like) aroma with cinnamon-like and cucumber undertones from a fragrance standpoint. The resulting substance has a green, melony, minty, herbaceous and floral aroma and taste profile at 2 ppm mking it useful for mint and peppermint flavors.

FIG. 21 is the GLC profile for the reaction product. The peak indicated by the reference numeral "51" is the peak for the reaction product defined according to the structures: ##STR115## (mixtures of compounds).

FIG. 22 is the NMR spectrum for peak "51" of the GLC profile of FIG. 21 for the mixture of compounds defined according to the structures: ##STR116##

FIG. 23 is the infra-red spectrum for peak "51" of the GLC profile of FIG. 21 for the mixture of compounds defined according to the structures: ##STR117##

EXAMPLE IX PREPARATION OF 1,2,3,4,4A,5,8,8A-OCTAHYDRO-3-METHYL-1,4:5,8 DIMETHANONAPHTHALENE-2-CARBOXALDEHYDE ##STR118##

Into a 2 liter autoclave is placed the following materials:

(a) Dicyclopentadiene: 400 grams

(b) Crotonaldehyde: 255 grams

(c) Toluene: 500 ml

The autoclave is sealed and heated to 225° C. at a pressure of 200-320 psig and maintained at a temperature of 25° C. at a pressure in the range of 200-320 psig for a period of three hours. At the end of the three hour period, the autoclave is depressurized and opened. The reaction mass is then distilled on a fractionation column yielding a product boiling at a temperature in the range of 92°-96° C. (vapor temperature) and a liquid temperature in the range of 126°-140° C. at 1.0 mm/Hg pressure.

The reaction product at that boiling point has a spicy, cinnamon-like aroma.

FIG. 24 is the GLC profile for the reaction product (conditions: SE-30 column programmed at 220° C. isothermal).

FIG. 25 is the NMR spectrum for the resulting reaction product at the foregoing boiling range.

FIG. 26 is the infra-red spectrum for the resulting reaction product at the above boiling range.

EXAMPLE X PREPARATION OF

1,2,3,4,4A,5,8,8A-OCTAHYDRO-2-METHYL-1,4:5,8-DIMETHANONAPHTHALENE-2-CARBOXALDEHYDE ##STR119##

Into a 200 ml autoclave is placed the following ingredients:

(i) 400 grams Dicyclopentadiene;

(ii) 255 grams of methacrolein; and

(iii) 500 ml toluene

The autoclave is sealed and heated to 225° C. and maintained at 225° C. and at a pressure of 200 psig for a period of three hours. At the end of the three hour period the autoclave is opened and the resulting product is fractionally distilled yielding the following fractions:

    ______________________________________                                                 Vapor   Liquid  Vacuum        Weight of                                Fraction                                                                               Temp.   Temp.   mm. Hg. Reflux                                                                               Fraction                                 No.     (°C.)                                                                           (°C.)                                                                           Pressure                                                                               Ratio (gm)                                     ______________________________________                                         1       27/57   23/90   2/2     9:1   21.1                                     2       70      126     2       9:1   11.5                                     3       75      132     2       9:1   13.7                                     4       83      135     2       9:1   17.2                                     5       83      135     2       9:1   13.5                                     6       85      136     2       9:1   23.5                                     7       85      136     2       9:1   24.8                                     8       85      136     2       9:1   26.1                                     9       85      176     2       9:1   18.7                                     10      86      136     2       9:1   17.8                                     11      86      136     2       1:1   33.1                                     12      86      137     2       1:1   30.6                                     13      86      137     2       1:1   29.8                                     14      86      137     2       1:1   31.3                                     15      86      137     2       1:1   32.0                                     16      86      140     2       1:1   33.1                                     17      86      140     2       1:1   29.6                                     18      86      140     2       1:1   29.0                                     19      87      140     2       --    32.1                                     20      85      143     2       --    33.3                                     21      80      186     2       --    30.1                                     ______________________________________                                    

Fractions 4-15 are bulked for subsequent evaluation for tobacco, food flavoring and fragrance properties.

EXAMPLE XI CHYPRE PERFUME FORMULATIONS

The following formulation is prepared:

    ______________________________________                                         Ingredients           Parts by Weight                                          ______________________________________                                         Texas Cedarwood Oil       200                                                  Patchouli Oil             50                                                   Vetiver Oil               30                                                   Bergamot Oil              150                                                  African Geranium Oil      50                                                   Coumarin                  60                                                   Natural Oak Moss          80                                                   Tolu Balsam Peru          200                                                  Labdanum                  150                                                  Musk Xylene               10                                                   Product of Example IV,                                                         bulked fractions 6-10                                                          consisting of the                                                              compound having the                                                            structure:                                                                      ##STR120##               135                                                  ______________________________________                                    

The addition of the compound having the structure: ##STR121## to this Chypre essence causes said Chypre to have an interesting sandalwood-like, patchouli-like and vetiver-like series of topnotes.

Accordingly, this formulation can be described as having a Chypre essence with patchouli-like, sandalwood-like and vetiver-like topnotes.

EXAMPLE XII PREPARATION OF HERBAL FRAGRANCES

The following mixtures are prepared:

                                      TABLE I                                      __________________________________________________________________________                             Parts by Weight                                        Ingredients             XIIA                                                                               XIIB                                                                               XIIC                                                                               XIID                                       __________________________________________________________________________     Amyl Cinnamic Aldehyde  20% 20% 20% 20%                                        Phenyl Acetaldehyde Dimethyl                                                                           4%  4%  4%  4%                                         Acetal                                                                         Thyme Oil, White        8%  8%  8%  8%                                         Sauge Sclaree French    8%  8%  8%  8%                                         Galbanum Oil            4%  4%  4%  4%                                         Geranyl Acetate         10% 10% 10% 10%                                        Juniper Berry Oil       4%  4%  4%  4%                                         Methyl Octin Carbonate  2%  2%  2%  2%                                         Linalyl Acetate         10% 10% 10% 10%                                        Dihydro Methyl Jasmonate                                                                               20% 20% 20% 20%                                        Fenchyl Ethyl Ether     10% 10% 10% 10%                                         ##STR122##             3%  0%  0%  0%                                          ##STR123##             0%  6%  0%  0%                                          ##STR124##             0%  0%  6%  0%                                          ##STR125##             0%  0%  0%  5%                                         __________________________________________________________________________

When added to this herbal formulation the product of Example I imparts to the herbal formulation a melony, cucumber, violet-like, wormwood-like and generally pleasant floral undertone.

The product of Example II when added to this herbal formulation imparts to it, a floral, melony and cinnamon-like undertones.

When the product of Example VI is added to this herbal formulation a pineapple-like, pleasant floral undertone is added to the herbal essence profile.

When the reaction product of Example VIII is added to this herbal formulation, animalic, leafy, floral, violet-like, cinnamon-like and cucumber-like undertones are imparted to this formulation.

EXAMPLE XIII PATCHOULI/SPICY PERFUME FORMULATION

The following mixture is prepared:

    ______________________________________                                         Ingredients              Parts by Weight                                       ______________________________________                                         Orange Oil                   50                                                Beramot Oil                  20                                                Lime Oil                     100                                               1-Hydroxy-methyl-2,4,6                                                                                      45                                                Trimethyl cyclohexane                                                          Neroli Oil                    5                                                4-(4-Methyl-4-Hydroxyamyl)                                                                                  10                                                Δ.sup.3 -cyclohexane carboxaldehyde                                      2,3,3A,4,5,7A-Hexahydro-6,7A,8,8-                                                                           100                                               Tetramethyl-1,5-methano-[1H]-inden-1-ol                                        1',2',3',4',5',6',7',8'-octahydro                                              2',3',8',8'-tetramethyl-2'-aceto-                                              naphthone isomer mixture produced                                              according to the process of  20                                                Example VII of the U.S.                                                        Letters Pat. No. 3,911,018                                                     issued on October 7, 1975                                                      Gamma Methyl Ionone          20                                                1-acetyl-2,5,5-trimethylcyclo-                                                                              100                                               heptane                                                                        Substituted tricyclodecane                                                     derivatives prepared according                                                 to Example XII of U.S. Pat.  100                                               No. 4,275,251 issued on                                                        June 23, 1981                                                                  Product of Example IX, supra,                                                  having the structure:                                                           ##STR126##                  85                                                ______________________________________                                    

The compound produced according to Example IX having the structure: ##STR127## imparts to this patchouli/spicy formulation an intense, cinnamon-like, long lasting, oriental, spicy characteristic.

EXAMPLE XIV PREPARATION OF SOAP COMPOSITION

A total of 100 grams of soap chips produced from unperfumed sodium base toilet soap made from talo and coconut oil is admixed with 1 gram of each of the perfume compositions set forth in Table II, below until a substantially homogeneous composition is obtained. The mixture is melted under 8 atmospheres pressure at 190° C. and maintained at 190° C. with mixing for a period of five hours at 8 atmospheres pressure. At the end of the five hour period, the resulting mixture is cooled and cut into soap bars. Each of the soap bars manifest an excellent aroma as set forth in Table II, supra:

                  TABLE II                                                         ______________________________________                                         Structure of Compound                                                          and example by which                                                           produced               Perfumery Profile                                       ______________________________________                                         Aldehyde produced      An herbal, strong,                                      according to Example I,                                                                               green, aldehydic,                                       bulked fractions 14-19,                                                                               wormwood-like and                                       having the structure:  floral aroma profile.                                    ##STR128##                                                                    Compound produced according                                                                           A melony,                                               to Example I, having the                                                                              cucumber-like,                                          structure:             violet-like, green,                                      ##STR129##            aldehydic aroma profile.                                bulked fractions 8-12.                                                         Compound produced according                                                                           A floral, melony,                                       to Example II, having the                                                                             cinnamon-like                                           structure:             aroma.                                                   ##STR130##                                                                    bulked fractions 7-13.                                                         Compound produced according                                                                           A sandalwood,                                           to Example IV, having the                                                                             patchouli, vetiver                                      structure:             aroma profile.                                           ##STR131##                                                                    bulked fractions 6-10.                                                         Compound produced according                                                                           A floral,                                               to Example VI, having the                                                                             pineapple-like                                          structure:             aroma profile.                                           ##STR132##                                                                    bulked fractions 8-10.                                                         Compound produced according                                                                           A sweaty, animal-                                       to Example VII, having the                                                                            like, musk-like                                         structure:             aroma profile.                                           ##STR133##                                                                    bulked fractions 1-5.                                                          A mixture of compounds An animalic, leafy,                                     produced according to  green, herbaceous,                                      Example VIII, containing                                                                              floral, violet-like                                     the compounds having   aroma with cinna-                                       structures:            mon-like and cu-                                                               cumber-like under-                                                             tones.                                                   ##STR134##                                                                    Compound produced according                                                                           A spicy,                                                to Example IX having the                                                                              cinnamon-like                                           structure:             aroma profile.                                           ##STR135##                                                                    Perfume composition of A chypre aroma                                          Example XI.            with patchouli-                                                                like, vetiver-like                                                             and sandalwood-                                                                like topnotes.                                          Perfume composition of A herbal aroma                                          Example XIIA.          with melony, cu-                                                               cumber, violet-like,                                                           wormwood-like and                                                              pleasant floral                                                                undertones.                                             Perfume composition of A herbal aroma                                          Example XIIB.          with floral, melony                                                            and cinnamon-like                                                              undertones.                                             Perfume composition of A herbal aroma                                          Example XIIC.          with floral and                                                                pineapple-like                                                                 undertones.                                             Perfume composition of A herbal essence                                        Example XIID.          with animal-like,                                                              leafy, floral, violet-                                                         like, cinnamon-like                                                            and cucumber                                                                   undertones.                                             Perfume composition of A patchouli/spicy                                       Example XIII.          formulation an                                                                 intense, cinnamon-                                                             like, long lasting,                                                            oriental, spicy                                                                characteristic.                                         ______________________________________                                    

EXAMPLE XV PREPARATION OF A DETERGENT COMPOSITION

A total of 100 grams of a detergent powder sold under the trademark "RINSO®" are mixed with 0.15 grams of each of the perfumery substances as set forth in Table II of Example XIV, supra, until a substantially homogeneous composition is obtained. Each of the detergent powders manifest an excellent aroma as set forth in Table II of Example XIV.

EXAMPLE XIV PREPARATION OF COSMETIC BASES

A cosmetic powder is prepared by mixing in a ball mill 100 grams of talcum powder with 0.25 grams of one of the perfumery substances as set forth in Table II of Example XVI. The cosmetic powders produced using the materials of Table II of Example XIV have aroma characteristics as set forth in Table II of Example XIV.

EXAMPLE XVII LIQUID DETERGENT COMPOSITION

Concentrated liquid detergents with aromas as set forth in Table II of Example XIV containing 0.2%, 0.5% and 1.2% of one of the substances set forth in Table II of Example XIV are prepared by adding appropriate quantities of perfumery substances as set forth in Table II of Example XIV to a liquid detergent known as P-87. The aroma intensity of each of the liquid detergents so prepared increases with increasing concentration of each of the substances as set forth in Table II of Example XIV, each of the detergents manifesting aromas as set forth in Table II of Example XIV.

EXAMPLE XVIII PREPARATION OF COLOGNES AND HANDKERCHIEF PERFUMES

Each of the perfume substances of Table II of Example XIV are incorporated into 80%, 85%, 90% and 95% foodgrade ethanol solutions at the rates of 2.0%, 2.5%, 3.0%, 3.5% and 4.0%; and into handkerchief perfumes at concentrations of 15%, 20%, 25%, 30% and 40% (in 80%, 85%, 90% and 95% aqueous foodgrade ethanol). These of each of the substances of Table II of Example XIV are for distinct and definitive aroma nuances in each of the handkerchief perfumes and colognes as indicated in Table II of Example XIV.

EXAMPLE XIX PREPARATION OF DETERGENT COMPOSITION

A total of 100 pounds of a detergent powder prepared according to U.S. Pat. No. 4,058,472 (the disclosure of which is incorporated by reference herein) and containing 5% by weight of the sodium salts of a mixture of sulfonated C₁₄ -C₁₈ alkyl catechol as a surface active component, the mixture being 60 parts by weight of mono-C₁₄ -C₁₈ alkyl catechol and 40 parts by weight of di-C₁₄ -C₁₈ alkyl catechol, 35% of sodium tetrapyrophosphate, 30% of sodium silicate, 20% of sodium carbonate, 3% of sodium carboxymethyl cellulose and 7% of starch is mixed with 0.15 grams of one of the perfumery substances set forth in Table II of Example XIV, supra, until substantially homogeneous compositions are obtained. Each of the compositions have excellent aromas as set forth in Table II of Example XIV.

EXAMPLE XX

Scented polyethylene pellets having pronounced aromas as set forth in Table II of Example XIV are prepared as follows:

75 pounds of polyethylene of a melting point of about 220° F. are heated to about 230° C. under 5 atmospheres pressure in a pressure vessel. 25 pounds of each of the substances set forth in Table II of Example XIV, separately, are then quickly added to the liquified polyethylene. The temperature is maintained at 230° C. under high pressure and the mixing is continued for about 15 minutes in each case. The pressure vessel is then depressurized and the molten polyethylene enriched with each of the perfumery substances is permitted to exit from the vessel by gravity. The liquid falling through orifices (in the apparatus) in droplets solidifies almost instantaneously on impact with a moving cooled conveyor operating immediately below the pressure vessel. Solid polyethylene pellets having pronounced aromas as set forth in Table II of Example XIV are thus formed. In each case 50 pounds of thus-formed master pellets are then added to 1000 pounds of unscented polyethylene powder and the mass is heated to the liquid state. The liquid is molded into thin sheets, films and container shapes. The thin sheets, films and container shapes have pronounced aromas as set forth in Table II of Example XIV.

EXAMPLE XXI

Utilizing the procedure of Example I at column 15 of U.S. Pat. No. 3,632,396 (the specification for which is incorporated by reference herein), a non-woven cloth substrate useful as a drier-added fabric softening article of manufacture is prepared wherein the substrate, the substrate coating and the outer coating and the perfuming material are as follows:

1. a water dissolvable paper as the substrate ("Dissolvo Paper");

2. Adogen 448 (melting point 140° F.) as the substrate coating; and

3. an outer coating having the following formulation (melting point about 150° F.):

57% C₂₀ -₂₂ HAPS

22% isopropyl alcohol

20% antistatic agent

1% of one of the perfumery substances as set forth in Table II of Example XIV.

A fabric softening composition prepared as set forth above having aroma characteristics as set forth in Table II of Example XIV consists of a substrate having a weight of about 3 grams per 100 square inches, a substrate coating weighing about 1.85 grams per 100 square inches of substrate and an outer coating weighing about 1.4 grams per 100 square inches of substrate is created, thereby providing a total aromatized substrate and outer coating weight ratio of about 1:1 by weight of the substrate. The aromas as set forth in Table II of Example XIV is imparted in pleasant manners to head spaces in the dryers on operation thereof using the drier-added fabric softening non-woven fabric articles.

EXAMPLE XXII VANILLA FLAVOR

The following formulation is prepared:

    ______________________________________                                         Vanillin               10.0   grams                                            Ethyl Vanillin         3.0    grams                                            Benzodihydropyrone     3.0    grams                                            Heliotropin            1.0    grams                                            Propenyl Guiacol       0.5    grams                                            Gamma Nonyl Lactone    0.25   grams                                            Gamma Undecalactone    0.25   grams                                            Delta-Dodecalactone    0.25   grams                                             ##STR136##             0.001  grams                                           ______________________________________                                    

The compound having the structure: ##STR137## enhances the foregoing vanillin formulation (a) making it more natural-like; and (b) making it three times (3×) as powerful as the formulation without this compound added thereto. In addition, the formulation is rendered much more outstanding in a standard creme-de-Kahlua formulation causing the creme-de-Kahlua formulation to be more natural-like and preferred by a bench panel of five members, unanimously. The resulting formulation containing the compound having the structure: ##STR138## is added to the following liqueur formulation:

    ______________________________________                                         Ingredients       Parts by Weight                                              ______________________________________                                         Clove essential oils                                                                             780                                                          Lemon essential oils                                                                             400                                                          Orange essential oils                                                                            300                                                          Cinnamon essential oils                                                                          250                                                          Mace essential oils                                                                              180                                                          Vanillin formulation                                                                             150                                                          (as set forth above)                                                           Neroli essential oil                                                                             10                                                           Citronellol       2                                                            Rose absolute     1                                                            Food grade ethanol                                                                               927                                                          ______________________________________                                    

The resulting liqueur is added to the following mixture in order to produce a consumable material:

    ______________________________________                                         Ingredients        Parts by Weight                                             ______________________________________                                         96% Food grade ethanol                                                                            301        kg                                               Sugar              40         kg                                               Distilled water    46.8       liters                                           Flavor (as set forth above)                                                                       0.5        kg                                               (0.5% in food grade ethanol)                                                   ______________________________________                                    

The resulting liquer has an interesting, bitter almond taste and aroma making it useful as such or as a "Bagne" for a sauce used for soaking pound cakes such as "Rum Baba".

EXAMPLE XXIII

The vanilla flavor of Example XII is placed into an ice cream mix at the rate of 0.05%. The resulting previously-unflavored ice cream has an excellent vanilla flavor.

EXAMPLE XXIV SALAD DRESSING

To a portion of essentially flavorless salad dressing, the compound of Example VII, having the structure: ##STR139## (bulked fractions 1-5) is added at the rate of 1 ppm and also at the rate of 2 ppm. The resulting mixtures have characteristic artichoke notes. The salad dressing is a mixture of the following:

    ______________________________________                                         Ingredient           Parts by Weight                                           ______________________________________                                         Black pepper oil     3                                                         Nutmeg oil           3                                                         Celery Oil           3                                                         Lemon oil            3                                                         Mustard oil          1                                                         Vinegar-citric acid (50--50 mixture)                                                                120                                                       Starch paste prepared from tapioca                                                                  300                                                       flour-water (50--50 mixture)                                                   Liquid egg yolks     210                                                       Sodium chloride      7                                                         Sucrose              10                                                        Mustard              20                                                        Locust Bean gum      6                                                         ______________________________________                                    

EXAMPLE XXV(A), (B) LEMON/FRUITY FLAVOR FORMULATION

The following lemony, fruity flavor formulations are prepared:

    ______________________________________                                                            Parts by Weight                                             Ingredient           XXV(A)     XXV(B)                                         ______________________________________                                         Natural Lemon Oil,    10.0      10.0                                           Terpeneless                                                                    Acetaldehyde         0.6        0.6                                            Alpha-terpineol      2.1        2.1                                            Citral               1.8        1.8                                            Carvone              0.24       0.24                                           Terpinolene          1.2        1.2                                            Alpha-terpinene      0.25       0.25                                           Diphenyl             0.25       0.25                                           Alpha Fenchyl Alcohol                                                                               0.25       0.25                                           Limonene             0.35       0.35                                           Linalool             0.25       0.25                                           Geranyl Acetate      0.25       0.25                                           Nootkatone           0.25       0.25                                           Neryl Acetate        0.25       0.25                                           Geranyl nitrile      0.55       0.55                                           Citronellyl nitrile  0.60       0.60                                           Fenchyl ethyl ether  0.05       0.05                                            ##STR140##           0.50       0.0                                            ##STR141##           0.0        0.75                                          ______________________________________                                    

The compound of Example II adds to this lemon flavor formulation an excellent melony flavor causing the overall formulation to have a "lemon/melon" aroma and taste causing it to be useful in enhancing the taste of fresh papaya fruit when three or four drops of this flavor diluted at the rate of 1% in 50% aqueous foodgrade ethanol is placed on the open papaya fruit.

The compound of Example VI adds an excellent pineapple aroma and taste nuance to this lemon flavor. When the flavor (in 2% dilution and 50% foodgrade ethanol) is added to cooking chicken, the resultant cooked chicken has an excellent "lemony nuance" which is enhanced by use of the compound of Example VI.

EXAMPLE XXVI ROOT BEER BEVERAGE

The compound having the structure: ##STR142## produced according to Example IV, bulked fractions 6-10 is added to root beer (Barrelhead, produced by Canada Dry Corporation of Maspeth, N.Y., a division of the Norton Simon Corporation) at the rate of 1.5 ppm and submitted to a bench panel. The tetracyclic carbinol improves the woody rooty notes insofar as the aroma and taste of the rootbeer are concerned. Therefore, the beverage containing the compound defined according to the structure: ##STR143## is preferred by a bench panel (of five members) unanimously over the beverage which does not contain the tetracyclic carbinol derivative produced according to Example IV.

EXAMPLE XXVII AMARETTO FLAVOR

The following formulation is prepared:

    ______________________________________                                         Ingredients            Parts by Weight                                         ______________________________________                                         Lavender essential oil 105.0                                                   Clary sage essential oil                                                                              100.0                                                   Rosemary essential oil 100.0                                                   Thyme essential oil    90.0                                                    Fennel essential oil   40.0                                                    Mint essential oil     20.0                                                     ##STR144##             5.9                                                    Angelica essential oil 5.0                                                     Anise essential oil    5.0                                                     Lemon essential oil    4.0                                                     Wormwood essential oil 2.0                                                     Cinnamon essential oil 0.1                                                     (10% in alcohol solution)                                                      Aqueous 95%, foodgrade ethanol                                                                        523.0                                                   ______________________________________                                    

The mixture of compounds produced according to Example VIII enhances this amaretto flavor in view of the green, melony, minty, herbaceous and floral aroma and taste nuances which particularly enhance the mint oil aroma and taste portion of this formulation.

A liqueur is produced by using the foregoing formulation as follows:

    ______________________________________                                         Ingredient         Parts by Weight                                             ______________________________________                                         96% alcohol            46.1        l                                           Sugar                  1.0         kg                                          Distilled Water        55.1        l                                           Amaretto flavor                                                                produced, supra                                                                (diluted at the rate   0.5         kg                                          of 0.8% in 95% aqueous                                                         foodgrade ethanol)                                                             ______________________________________                                    

In addition, the wormwood essential oil component of the foregoing amaretto flavor can be replaced totally by the use of the compound of Example I having the structure: ##STR145## bulked fractions 8-19. Actually the aldehyde having the structure: ##STR146## can replace the 2 parts by weight of wormwood essential oil by using only 0.02 parts by weight of the aldehyde having the structure: ##STR147##

EXAMPLE XXVIII TOOTHPASTE FLAVOR FORMULATION

The following basic toothpaste flavor formulation is prepared:

    ______________________________________                                         Ingredients    Parts by Weight                                                 ______________________________________                                         Cardamon Oil   0.2                                                             Clove Oil      1.0                                                             Spearmint Oil  2.0                                                             Peppermint Oil 96.8                                                            ______________________________________                                    

This flavor formulation is divided into three portions. To the first portion, nothing is added. To the second portion, 8 parts by weight of the first portion is combined with 2 parts by weight of anethole. Eight parts by weight of the third portion of this flavor is then combined with 2 parts by weight of the compound of Example IX having the structure: ##STR148## prepared according to Example IX and 2 parts by weight of anethole.

Each of the three flavors are compared in water at the rate of 10 ppm and evaluated by a bench panel. Each of the second and third flavors has sweet anise-like characteristics, but the flavor containing the compound defined according to the structure: ##STR149## also has cinnamic and spicy aroma and taste nuances. Therefore, the flavor containing the aldehyde produced according to Example IX is preferred over flavors not containing the aldehyde of Example IX and, in addition, the aldehyde of Example IX having the structure: ##STR150## augments and enhances the anise-like flavor.

EXAMPLE XXIX MINT FLAVOR FORMULATION

The following mint flavor formulation is prepared:

    ______________________________________                                         Ingredients             Parts by Weight                                        ______________________________________                                         Peppermint Oil          60.0                                                   Spearmint Oil           38.0                                                    ##STR151##             2.0                                                    ______________________________________                                    

The mixture of compounds produced according to Example VIII imparts a minty, herbaceous, floral, green and melony aroma and taste nuance of great intensity to this mint flavor formulation.

EXAMPLE XXX A. POWDER FLAVOR FORMULATION

20 Grams of the flavor composition of Example XXIX is emulsified in a solution containing 300 gm gum acacia and 700 gm water. The emulsion is spray-dried with a Bowen Lab Model Drier utilizing 260 c.f.m. of air with an inlet temperature of 500° F., an outlet temperature of 200° F. and a wheel speed of 50,000 rpm.

B. SUSTAINED RELEASE FLAVOR

The following mixture is prepared:

    ______________________________________                                         Ingredients             Parts by Weight                                        ______________________________________                                         Liquid mint Flavor          20.0                                               Composition of Example XXIX                                                    Propylene glycol            9.0                                                Cab-O-Sil ® M-5                                                            (Brand of Silica produced                                                      by the Cabot Corporation                                                       of 125 High Street,                                                            Boston, Mass. 02110;        5.00                                               Physical Properties:                                                           Surface Area: 200 m.sup.2 gm                                                   Nominal particle size: 0.012 microns                                           Density: 2,3 lbs/cu. ft.)                                                      ______________________________________                                    

The Cab-O-Sil is dispersed in the liquid mint flavor composition of Example XXIX with vigorous stirring, thereby resulting in a viscous liquid. 71 Parts by weight of the powder flavor composition of Part A of this example, supra, is then blended into the said viscous liquid, with stirring, at 25° C. for a period of 30 minutes resulting in a dry, free flowing sustained release flavor powder.

EXAMPLE XXXI

10 Parts by weight of 50 Bloom pigskin gelatin is added to 90 parts by weight of water at a temperature of 150° F. The mixture is agitated until the gelatin is completely dissolved and the solution is cooled to 120° F. 20 Parts by weight of the liquid flavor composition of Example XXIX is added to the solution which is then homogenized to form an emulsion having particle size typically in the range of 5-40 microns. This material is kept at 120° F. under which conditions the gelatin will not jell.

Coacervation is induced by adding slowly and uniformly 40 parts by weight of a 20% aqueous solution of sodium sulphate. During coacervation the gelatin molecules are deposited uniformly about each oil droplet as a nucleus.

Gelation is effected by pouring the heated coacervate mixture into 1,000 parts by weight of 7% aqueous solution of sodium sulphate at 65° F. The resulting jelled coacervate may be filtered and washed with water at temperatures below the melting point of gelatin, to remove the salt.

Hardening of the filtered cake, in this example, is effected by washing with 200 parts by weight of 37% solution of formaldehyde in water. The cake is then washed to remove residual formaldehyde.

EXAMPLE XXXII CHEWING GUM

100 Parts by weight of chicle are mixed with 4 parts by weight of the flavor prepared in accordance with Example XXIX. 300 Parts of sucrose and 100 parts of corn syrup are added. Mixing is effected in a ribbon blender with jacketed side walls of the type manufactured by the Baker Perkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inch in width and 0.1 inches in thickness. The strips are cut into lengths of 3 inches each. On chewing, the chewing gum has a pleasant, long lasting mint flavors.

EXAMPLE XXXIII CHEWING GUM

100 Parts by weight of chicle are mixed with 18 parts by weight of the flavor prepared in accordance with Example XXX(B). 300 Parts of sucrose and 100 parts of corn syrup are then added. Mixing is effected in a ribbon blender with jacketed side walls of the type manufactured by the Baker Perkins Co.

The resultant chewing gum blend is then manufactured into strips 1 inch in width and 0.1 inches in thickness. The strips are cut into lengths of 3 inches each. On chewing, the chewing gum has a pleasant, long lasting mint flavor.

EXAMPLE XXXIV TOOTHPASTE FORMULATION

The following separate groups of ingredients are prepared:

    ______________________________________                                         Parts by Weight   Ingredients                                                  ______________________________________                                         Group "A"                                                                      30.200            Glycerine                                                    15.325            Distilled Water                                              .100              Sodium Benzoate                                              .125              Saccharin Sodium                                             .400              Stannous Fluoride                                            Group "B"                                                                      12.500            Calcium Carbonate                                            37.200            Dicalsium Phosphate                                                            (Dihydrate)                                                  Group "C"                                                                      2.000             Sodium N--Lauroyl                                                              Sarcosinate (foaming                                                           agent)                                                       Group "D"                                                                      1.200             Flavor Material of                                                             Example XXX(B)                                               100.00 TOTAL                                                                   ______________________________________                                          PROCEDURE:                                                                     1. The ingredients in Group "A" are stirred and heated in a steam jackete      kettle to 160° F.;                                                      2. Stirring is continued for an additional three to five minutes to form       homogeneous gel;                                                               3. The powders of Group "B" are added to the gel, while mixing, until a        homogeneous paste is formed;                                                   4. With stirring, the flavor of "D" is added and lastly the                    sodiumn-lauroyl sarcosinate; and                                               5. The resultant slurry is then blended for one hour. The completed paste      is then transferred to a three roller mill and then homogenized, and           finally tubed.                                                           

The resulting toothpaste when used in a normal toothbrushing procedure yields a pleasant mint flavor, of constant strong intensity throughout said procedure (1-1.5 minutes).

EXAMPLE XXXV CHEWABLE VITAMIN TABLETS

The flavor material produced according to the process of Example XXX(B) is added to a Chewable Vitamin Tablet. Formulation at a rate of 10 gm/Kg which Chewable Vitamin Tablet formulation is prepared as follows:

In a Hobart mixer, the following materials are blended to homogeneity:

    ______________________________________                                                              Gms/1000 Tablets                                          ______________________________________                                         Vitamin C (ascorbic acid) as                                                                          70.11                                                   Ascorbic acid-sodium ascorbate                                                                        4.0                                                     mixture 1:1                                                                    Vitamin B.sub.1 (thiamine mononitrate) as                                      Rocoat ® thiamine mononitrate                                                                     5.0                                                     331/3% (Hoffman LaRoche)                                                       Vitamin B.sub.2 (riboflavin) as                                                Rocoat ® riboflavin 331/3%                                                                        4.0                                                     Vitamin B.sub.6 (pyridoxine hydrochloride) as                                  Rocoat ® pyridoxine hydrochloride                                                                 33.0                                                    331/3%                                                                         Niacinamide as Rocoat ® niacinamide                                        331/3%                                                                         Calcium pantothenate   11.5                                                    Vitamin B.sub.12 (cyanocobalamin) as                                                                  3.5                                                     Merck 0.1% in gelatin                                                          Vitamin E (dl-alpha tocopheryl                                                                        6.6                                                     acetate) as dry Vitamin E acetate 331/3%                                       d-Biotin               0.044                                                   Flavor of Example XXX(B)                                                                              (as indicated above)                                    Certified lake color   5.0                                                     Sweetener - sodium saccharin                                                                          1.0                                                     Magnesium stearate lubricant                                                                          10.0                                                    Mannitol q.s. to make  500.0                                                   ______________________________________                                    

Preliminary tablets are prepared by slugging with flatfaced punches and grinding the slugs to 14 mesh. 13.5 gm dry Vitamin A Acetate and 0.6 gm Vitamin D are then added as beadlets. The entire blend is then compressed using concave punches at 0.5 gm each.

Chewing of the resultant tablets yields a pleasant, long-lasting mint flavor for a period of 15 minutes.

EXAMPLE XXVI CHEWING TOBACCO

Onto 100 pounds of tobacco for chewing (85% Wisconsin leaf and 15% Pennsylvania leaf) the following casing is sprayed at a rate of 30%:

    ______________________________________                                         Ingredients     Parts by Weight                                                ______________________________________                                         Corn Syrup      60.0                                                           Licorice        10.0                                                           Glycerine       20.0                                                           Fig Juice       4.6                                                            Prune Juice     5.0                                                            Mint flavor of  0.08                                                           Example XXX (I)                                                                ______________________________________                                    

The resultant product is redried to a moisture content of 20%. On chewing, this tobacco has an excellent cooling mint flavor nuance in conjunction with the tobacco notes.

EXAMPLE XXXVI TOBACCO FORMULATION

A tobacco blend is made up by mixing the following materials:

    ______________________________________                                         Ingredient      Parts by Weight                                                ______________________________________                                         Bright          40.1                                                           Burley          24.9                                                           Maryland         1.1                                                           Turkish         11.6                                                           Stem (flue cured)                                                                              14.2                                                           Glycerine        2.8                                                           Water            5.3                                                           ______________________________________                                    

The above tobacco is ued in producing cigarettes, and the following formulation is compounded and incorporated into each of these cigarettes:

    ______________________________________                                         Ingredient     Parts by Weight                                                 ______________________________________                                         Ethyl butyrate  0.05                                                           Ethyl valerate  0.05                                                           Maltol          2.00                                                           Cocoa extract  26.00                                                           Coffee extract 10.00                                                           Ethyl alcohol  20.00                                                           Water          41.90                                                           ______________________________________                                    

The above flavor is incorporated into model "filter" cigarettes at the rate of 0.1%.

One-fourth of these model cigaretts are treated in the tobacco section with the mixture of aldehydes produced according to Example VIII having the structures: ##STR152##

One-fourth of these model cigarettes are treated in the tobacco section with the compound defined according to the structure: ##STR153## produced according to Example IX.

Each of the foregoing aldehydes is added at rates of 100, 200 and 300 ppm per cigarette.

Another one-fourth of these model cigarettes are treated in the filter with either the mixture of aldehydes of Example VIII or the aldehyde of Example IX at the rate of 2×10⁻⁵ gm per gm of filter.

When evaluated by paired comparison, the cigarettes treated both in the tobacco and the filter with the mixture of compounds produced according to Example VIII are found, in smoke flavor, to have sweet, floral, green, herbaceous, minty and cooling aroma and taste nuances, and also cause the tobacco to be more natural-like. Also an excellent hay tobacco aroma and taste is imparted prior to and on smoking in both the main stream and the side stream by the product of Example VIII.

When evaluated by a paired comparison, these cigarettes are treated in both the tobacco and the filter with the compound of Example IX are found in smoked flavored to have oriental, spicy, cinnamon-like aroma and taste nuances causing the tobacco to be "oriental" and also natural in its "oriental" character. In general, an excellent "Turkish" tobacco aroma and taste is imparted prior to and on smoking in the main stream and in the side stream by the product produced according to Example IX, supra. 

What is claimed is:
 1. The compound having the structure: ##STR154##
 2. The compound having the structure: ##STR155##
 3. The compound having the structure: ##STR156## 